1. Field of the Invention
This invention describes a viscoelastomeric material with high shear at ambient and elevated temperatures prepared from a blend of ethylenically unsaturated monomers. A process for making this material is also described.
2. Background Information
Pressure sensitive adhesives (PSAs) made by photopolymerizing an alkyl acrylate and a polar copolymerizable monomer are known in the art. See, e.g., U.S. Pat. Nos. RE 24,906; 4,181,755; 4,364,972; and 4,243,500. Acrylic-based PSAs exhibit good adherence to high energy (i.e., polar) substrates such as metal and painted steel surfaces but generally exhibit lower adhesion to low energy (i.e., nonpolar) substrates such as polyethylene and polypropylene.
Solvent-processed acrylic PSA compositions can be crosslinked by adding a polyfunctional crosslinking agent that reacts with a reactive group present in the polymer. See, e.g., Japanese Kokoku 581983!-046236 in which is described a solvent-processed crosslinked acrylic PSA with excellent cohesion that is the reaction product of (a) a polyisocyanate, prepared by reacting (1) an acrylic copolymer having a molecular weight between 1,000 and 30,000 and from 1.7 to 5.0 functional groups that can react with an isocyanate group with (2) a diisocyanate, so that the ratio of isocyanate groups per coreactive functional group is about 2:1, and (b) an adherent copolymer comprising functional groups that can react with an isocyanate group. Like any solvent processing technique, however, the preparation of thick adhesives is difficult because the solvent causes bubbling in the adhesive and the emission of solvent vapors into the atmosphere is undesirable.
To avoid environmental pollution, manufacturing processes that do not require the use of volatile solvents have become of great interest. An early step in this direction for the manufacture of PSA tape was the process described in Belgium Patent No. 675,420. In this process, flexible carriers are coated with acrylic monomers, or mixtures of such monomers with copolymerizable compounds, with the possible addition of a thickening and/or initiating agent, and the monomers are polymerized directly on the carrier using ultraviolet radiation.
Hot melt coating a PSA composition eliminates the necessity of solvent processing. To hot melt process an adhesive composition, the composition must be uncrosslinked during the coating process; however, to achieve a PSA with balanced properties (i.e., peel and shear adhesion), the composition must be crosslinked. In hot melt coating processes, this is usually done by exposure to high energy radiation (e.g., E-beam or high intensity ultraviolet radiation). When high intensity ultraviolet radiation is used, a photoactive crosslinking species such as benzophenone is generally added to the composition. However, this often results in PSAs that display cure gradients. Additionally, thicker sections of PSA compositions cannot be cured this way.
A more efficient method of photocrosslinking involves incorporating hydrogen abstracting moieties into the polymer backbone prior to coating. Such polymers can be hot melt coated and subsequently cured by conventional irradiation techniques. This process is typified by U.S. Pat. No. 4,737,599 where a PSA with good adhesion to skin is described. That process is much more efficient than the high intensity irradiation method described immediately above, but the preparation of a thick PSA section that does not display a cure gradient is not described.
The cohesive strength of an acrylic PSA can be increased without unduly affecting its compliance by utilizing a photoactive crosslinking agent in conjunction with a photoinitiator. See, e.g., U.S. Pat. Nos. 4,181,752; 4,329,384; 4,330,590; 4,391,687, and 5,202,361. Useful photoactive crosslinking agents include various aldehydes, quinones, and particularly certain chromophore-substituted halomethyl-s-triazines (because they provide desirably shortened reaction times and somewhat greater tolerance to oxygen over the non-halomethyl-containing agents), although their use can result in evolution of HCl during polymerization.
An ultraviolet (UV) radiation-curable composition that includes 20 to 99% (by wt.) of a copolymer of ethylenically unsaturated monomers, 1 to 80% (by wt.) ethylenically unsaturated monomers, and 0 to 20% (by wt.) of one or more polyethylenically unsaturated compounds is described in U.S. Pat. No. 5,180,756.
Copolymerizable photoinitiators such as 2-4-(2-hydroxy-2,2-dimethyl-1-oxopropyl)phenoxy!ethyl 2-propenoate and their use in the polymerization of ethylenically unsaturated compounds is disclosed in U.S. Pat. No. 4,922,004.
Japanese Kokai 21990!-248482 describes a photocurable PSA obtained by reacting (a) 30 to 50 parts by weight (pbw) of a copolymer of an acrylic acid alkyl ester, a copolymerizable ethylenically unsaturated monomer having a polar group, and a copolymerizable monomer with a photosensitizing group (such as 2-acryloyloxybenzophenone or 1-acryloyloxy-2-4-(4-chlorobenzoyl)benzoyloxy!ethane); (b) 40 to 60 pbw of an aryloxy acrylic monomer such as phenoxyethyl acrylate or nonylphenoxyethyl acrylate; and (c) a tackifying resin. The composition is cured using a total dose of energy of 300 to 800 mJ/cm.sup.2 from a high pressure mercury lamp. Such high intensity ultraviolet radiation is likely to produce an adhesive that has a shear value less than 100 minutes.
Similarly, DE 42 03 183 C1 (Germany) discloses a method for producing PSA layers comprising the steps of thickening a monomer mixture that includes a photoinitiator with a separately made, solvent-free saturated UV-reactive polyacrylate; coating the thickened mixture onto a substrate; and irradiating the coated substrate. The separately made polymer comprises side chains that, when irradiated, participate in crosslinking reactions. The sole example involves the addition of a commercially available polymer having a molecular weight of about 200,000 to a monomer mixture that is then polymerized.
The shear values of PSAs prepared by actinically irradiating acrylic monomers can be enhanced by the addition of polyacrylic crosslinking agents. See, e.g., U.S. Pat. No. 4,379,201. Such PSAs involve networks and are sensitive to processing conditions.
A composition that can be radiation cured to provide thick, high molecular weight PSA compositions with outstanding properties has not been previously described.